CN115178107B - Method for preparing MOF-303/AAO composite membrane by hydrothermal self-growth and application thereof - Google Patents
Method for preparing MOF-303/AAO composite membrane by hydrothermal self-growth and application thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a MOF-303/AAO composite film by hydrothermal self-growth and application thereof, and relates to the technical field of composite materials. The porous anodic aluminum oxide nano channel membrane is used as a matrix, so that a powerful support is provided for the preparation of the composite membrane, and the closely ordered micro-nano pore channel structure can also endow the prepared MOF-303/AAO composite membrane with rapid directional solution transmission when the membrane is used as a filtering membrane; the MOF-303/AAO composite membrane prepared by the method has the advantages of strong overall performance, tight combination of the MOF-303 and the AAO nano-channel membrane, difficult falling off, easy achievement of synthesis conditions, simple preparation process, low raw material cost and small environmental pollution.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a method for preparing a MOF-303/AAO composite film by hydrothermal self-growth and application thereof.
Background
Metal Organic Frameworks (MOFs) are composed of metal clusters and organic linkers, and as a porous crystalline material, have been attracting attention due to their design-adjustable structure and pore size structure, and their ease of functionalization also confers great development potential. MOFs materials exhibit a great variety in chemical composition and topology due to their structural specificity. In recent years, with the continuous development of synthetic technology, MOFs are more and more abundant in variety, and have wide application prospects in the fields of gas storage, ion selective separation, sensing, catalysis, proton conduction and the like.
MOF-303 [Al(OH)(HPDC), HPDC= 1H-pyrazole-3,5-dicarboxylate]As a newly discovered MOF material in recent years, the material is made of Al 3+ And organic ligand HPDC, with xhh topology. Al (Al) 3+ Under the action of the octahedral coordination characteristic, the metal ion is bridged with four carboxyl groups and is connected with two carboxyl groups by sharing angles, so that the connection between the metal ion and the organic ligand is realized. With this infinitely extended connection, a rod-like Al (OH) (-COO) is formed 2 Clusters. The three-dimensional framework of MOF-303 extends along the a-axis to form a diamond-shaped channel (6A) with a one-dimensional structure, and the pore size of the diamond-shaped channel is between the diameter of water molecules (2.8A) and the diameter of common hydrated ions (more than or equal to 6.6A). The carboxyl functional group carried by the organic ligand provides a hydrophilic site for the one-dimensional channel, which is beneficial to quick passing of water molecules. By combining the pore size, the selective screening of water molecules can be realized by utilizing the size screening effect, and the method has wide application prospect and development value in the fields of sea water desalination, sewage treatment and the like.
MOFs materials are usually present in powder form, and loose physical structure is detrimental to their practical application. The most common coating method is generally to disperse the MOF in the binder, uniformly coat the surface of the substrate, and form a MOF film layer. The method is simple to operate and high in film forming speed, but the uniformity and compactness of the film are general, and the application requirements of the high-density MOF film are difficult to meet. The mixed matrix film rule is to add MOF as a rigid crystal material into a flexible polymer to prepare a composite material, and artificially endow the composite material with flexible and extensible external environment, so that the composite material presents a continuous and compact film structure in practical application, and the flexible change of the shape is realized by means of good plasticity of the polymer while the performance of the MOF material is maintained. However, this method has some disadvantages, such as poor compatibility of MOF and polymer, aggregation of MOF particles, easy swelling of polymer matrix after contact with organic solvent, and membrane structural failure, which limits its application to some extent. In addition, there are also methods of independently making pure MOF films, but the structural instability and poor mechanical properties of pure MOF films severely limit their practical application.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing an MOF-303/AAO composite film by hydrothermal self-growth.
The aim of the invention is achieved by the following technical scheme: a method for preparing MOF-303/AAO composite membrane by hydrothermal self-growth takes a porous anodic alumina nano channel membrane as a substrate, takes 3, 5-pyrazole dicarboxylic acid monohydrate, sodium hydroxide or/and aqueous solution of hydrochloric acid as a reaction solution, and carries out hydrothermal synthesis reaction at 80-120 ℃ to prepare the MOF-303/AAO composite membrane.
As a preferred scheme, the method takes a porous anodic aluminum oxide nano channel membrane as a substrate, takes a water solution of 3, 5-pyrazole dicarboxylic acid monohydrate, sodium hydroxide and hydrochloric acid as a reaction solution, and carries out hydrothermal synthesis reaction at the temperature of 80-120 ℃ to prepare the MOF-303/AAO composite membrane. The addition of sodium hydroxide in the reaction solution can promote the dissolution of the organic ligand 3, 5-pyrazole dicarboxylic acid monohydrate in water, and the addition of hydrochloric acid is used for adjusting the pH value of the reaction solution, so that the whole reaction environment is in an acidic condition, and the precipitation of Al in an AAO film is facilitated 3+ 。
Further, the preparation method specifically comprises the following steps:
s1, manufacturing a die: taking two polytetrafluoroethylene plates with the same size, wherein a round hole is formed in the middle of one polytetrafluoroethylene plate;
s2, pretreatment of a matrix film: cutting the porous anodic aluminum oxide nano channel membrane to be the same as the polytetrafluoroethylene plate in size and attaching, and cleaning and drying the porous anodic aluminum oxide nano channel membrane by using acetone, absolute ethyl alcohol and deionized water in sequence respectively;
s3, packaging: placing the pretreated porous anodic aluminum oxide nano-channel film between two polyethylene plates, enabling the bottom side of the porous anodic aluminum oxide nano-channel film to face to the open pore, and sealing the peripheries of the two plates by using a polytetrafluoroethylene adhesive tape;
s4, soaking and etching: adding a reaction solution into the reaction kettle, immersing the die packaged in the step S3 into the reaction kettle, sealing the reaction kettle and standing;
s5, hydrothermal self-growth: and heating the reaction kettle to carry out hydrothermal synthesis reaction, and cooling to room temperature after the reaction to obtain the MOF-303/AAO composite membrane.
Further, the concentration of hydrochloric acid in the reaction solution is 0-0.0217 mol/L, and the concentration of sodium hydroxide is 0-0.05556 mol/L.
Further, the concentration of the 3, 5-pyrazoledicarboxylic acid monohydrate is 0.01 to 0.03mol/L.
Further, the reaction time of the hydrothermal synthesis reaction is 24-56 h.
Further, the pore diameter of the porous anodic aluminum oxide nano-channel membrane is less than 200nm.
Further, the standing time in the step S4 is 0 to 8 hours.
It is another object of the present invention to provide the use of the MOF-303/AAO composite membrane prepared by the above method in directional rapid filtration.
The invention has the following advantages:
1. the invention adopts the porous Anodic Aluminum Oxide (AAO) nano channel membrane as a matrix, provides powerful support for the preparation of the MOF-303/AAO composite membrane, and can also endow the prepared MOF-303/AAO composite membrane with a tightly ordered micro-nano pore structure for directional and rapid solution transmission when the MOF-303/AAO composite membrane is used as a filtering membrane;
2. compared with the conventional MOFs material synthesis method, the method does not independently introduce metal salt as a metal ion source, but utilizes the Al separated out from the hydrothermal reaction solution by the porous Anodic Aluminum Oxide (AAO) nano-channel film 3+ Forming coordination with the organic ligand to complete nucleation and growth of MOF-303;
3. compared with the organic ligand which needs organic solution DMF as a reaction solvent in the preparation process of most MOF materials, the preparation cost is greatly reduced, and the injury to operators and the pollution to the environment in the preparation process are reduced;
4. according to the method, a hydrothermal method and an in-situ growth method are combined, a porous Anodic Aluminum Oxide (AAO) nano channel film is used as a matrix to prepare the MOF-303/AAO composite film, the synthesis conditions are easy to achieve, the preparation process is simple, the operation is easy, the synthesized MOF-303/AAO composite film is compact in structure, uniform in thickness and few in defects, and the MOF-303 is used as a microporous crystal material, so that the MOF-303 has great potential in the fields of sea water desalination, sewage treatment and the like due to the fact that the proper one-dimensional pore channel specification and hydrophilic functional group composition are adopted. Due to the process specificity, the MOF-303/AAO composite membrane prepared by the method has strong overall performance, and the MOF-303 and the AAO nano-channel membrane are tightly combined and are not easy to fall off, so that the applicability of the MOF-303/AAO composite membrane is ensured.
Drawings
FIG. 1 is a schematic diagram of the hydrothermal in situ self-growth process of the method of the present invention.
FIG. 2 is a plan view of a MOF-303/AAO composite film scanning electron microscope prepared by the method of the invention.
FIG. 3 is a cross-sectional view of a MOF-303/AAO composite film scanning electron microscope prepared by the method of the present invention.
FIG. 4 is a Scanning Electron Microscope (SEM) image of pure MOF-303 powder prepared in Experimental example 2.
FIG. 5 is a Fourier infrared spectrum of the MOF-303/AAO composite film, AAO film prepared by the method of the invention and pure MOF-303 powder prepared by experimental example 2.
FIG. 6 is an X-ray diffraction pattern of the MOF-303/AAO composite film, AAO film and pure MOF-303 powder prepared in experimental example 2 prepared by the method of the present invention, wherein 1 represents the MOF-303/AAO composite film, 2 represents the pure MOF-303 powder and 3 represents the AAO film.
FIG. 7 is an EDS spectrum and an atomic percent cake chart of the MOF-303/AAO composite film prepared by the method of the invention.
Fig. 8 is a mold diagram mentioned in the method of the present invention, wherein 1 is a clamping plate mold before assembly and 2 is an assembled mold.
Detailed Description
The invention will be further described with reference to the accompanying drawings and examples, to which the scope of the invention is not limited:
the principle of the method is shown in figure 1, a porous Anodic Aluminum Oxide (AAO) nano-channel film is taken as a composite film growth substrate, and is packaged in a special clamping plate die and vertically immersed in a hydrothermal reaction solution. The AAO film precipitates Al, especially in acidic hydrothermal reaction solutions 3+ And reacting with 3, 5-pyrazoledicarboxylic acid in the solution to generate MOF-303 crystals on the surface of the film and continuously growing.
Meanwhile, in the process, the AAO film provides a powerful support for the preparation of the MOF-303 composite film, and the closely ordered micro-nano pore canal structure provides enough nucleation sites for the growth of the MOF-303, so that the uniform growth of MOF-303 crystals is ensured, and the uniform and compact composite film is obtained.
Example 1: a method for preparing MOF-303/AAO composite membrane by hydrothermal self-growth uses porous anodic alumina nano channel membrane as substrate, pore diameter of the porous anodic alumina nano channel membrane is less than 200nm, aqueous solution of 3, 5-pyrazole dicarboxylic acid monohydrate, sodium hydroxide and hydrochloric acid is reaction solution, concentration of the 3, 5-pyrazole dicarboxylic acid monohydrate is 0.01mol/L, concentration of hydrochloric acid is 0.0217 mol/L, concentration of sodium hydroxide is 0.05556 mol/L, hydrothermal synthesis reaction is carried out for 24h under 80 ℃ condition, and MOF-303/AAO composite membrane is prepared.
Example 2: a method for preparing MOF-303/AAO composite membrane by hydrothermal self-growth uses porous anodic alumina nano channel membrane as substrate, pore diameter of the porous anodic alumina nano channel membrane is less than 200nm, aqueous solution of 3, 5-pyrazole dicarboxylic acid monohydrate and sodium hydroxide is reaction solution, concentration of the 3, 5-pyrazole dicarboxylic acid monohydrate is 0.03mol/L, concentration of the sodium hydroxide is 0.01mol/L, hydrothermal synthesis reaction is carried out for 56h at 120 ℃ to obtain MOF-303/AAO composite membrane.
Example 3: a method for preparing MOF-303/AAO composite membrane by hydrothermal self-growth uses porous anodic alumina nano channel membrane as substrate, pore diameter of the porous anodic alumina nano channel membrane is less than 200nm, aqueous solution of 3, 5-pyrazole dicarboxylic acid monohydrate and hydrochloric acid is reaction solution, concentration of the 3, 5-pyrazole dicarboxylic acid monohydrate is 0.02mol/L, concentration of hydrochloric acid is 0.02mol/L, hydrothermal synthesis reaction is carried out for 35h at 100 ℃ to obtain MOF-303/AAO composite membrane.
Example 4: a method for preparing a MOF-303/AAO composite film by hydrothermal self-growth, which specifically comprises the following steps:
s1, manufacturing a die: taking two polytetrafluoroethylene plates with the same size, wherein a round hole is formed in the middle of one polytetrafluoroethylene plate;
s2, pretreatment of a matrix film: cutting the porous anodic aluminum oxide nano-channel membrane with the aperture less than 200nm to be the same as the polytetrafluoroethylene plate in size and attaching, and cleaning and drying the porous anodic aluminum oxide nano-channel membrane by acetone, absolute ethyl alcohol and deionized water in sequence respectively;
s3, packaging: placing the pretreated porous anodic aluminum oxide nano-channel film between two polyethylene plates, enabling the bottom side of the porous anodic aluminum oxide nano-channel film to face to the open pore, and sealing the peripheries of the two plates by using a polytetrafluoroethylene adhesive tape;
s4, soaking and etching: adding an aqueous solution of 3, 5-pyrazole dicarboxylic acid monohydrate, hydrochloric acid and sodium hydroxide with the concentration of 0.01mol/L, 0.015 mol/L and 0.035 mol/L into a reaction kettle, and immersing the die packaged in the step S3 into the reaction kettle;
s5, hydrothermal self-growth: heating the reaction kettle to 110 ℃ for hydrothermal synthesis reaction, wherein the reaction time is 28h, and cooling to room temperature after the reaction to obtain the MOF-303/AAO composite membrane.
Example 5: a method for preparing a MOF-303/AAO composite film by hydrothermal self-growth, which specifically comprises the following steps:
s1, manufacturing a die: taking two polytetrafluoroethylene plates with the same size, wherein a round hole is formed in the middle of one polytetrafluoroethylene plate;
s2, pretreatment of a matrix film: cutting the porous anodic aluminum oxide nano-channel membrane with the aperture less than 200nm to be the same as the polytetrafluoroethylene plate in size and attaching, and cleaning and drying the porous anodic aluminum oxide nano-channel membrane by acetone, absolute ethyl alcohol and deionized water in sequence respectively;
s3, packaging: placing the pretreated porous anodic aluminum oxide nano-channel film between two polyethylene plates, enabling the bottom side of the porous anodic aluminum oxide nano-channel film to face to the open pore, and sealing the peripheries of the two plates by using a polytetrafluoroethylene adhesive tape;
s4, soaking and etching: adding an aqueous solution of 3, 5-pyrazole dicarboxylic acid monohydrate with the concentration of 0.02mol/L and hydrochloric acid with the concentration of 0.02mol/L into a reaction kettle, immersing the die packaged in the step S3 into the reaction kettle, sealing the reaction kettle, and standing for 8 hours;
s5, hydrothermal self-growth: heating the reaction kettle to 112 ℃ for hydrothermal synthesis reaction for 40 hours, and cooling to room temperature after the reaction to obtain the MOF-303/AAO composite membrane.
Example 6: a method for preparing a MOF-303/AAO composite film by hydrothermal self-growth, which specifically comprises the following steps:
s1, manufacturing a die: taking two polytetrafluoroethylene plates with the same size, wherein a round hole is formed in the middle of one polytetrafluoroethylene plate;
s2, pretreatment of a matrix film: cutting the porous anodic aluminum oxide nano-channel membrane with the aperture less than 200nm to be the same as the polytetrafluoroethylene plate in size and attaching, and cleaning and drying the porous anodic aluminum oxide nano-channel membrane by acetone, absolute ethyl alcohol and deionized water in sequence respectively;
s3, packaging: placing the pretreated porous anodic aluminum oxide nano-channel film between two polyethylene plates, enabling the bottom side of the porous anodic aluminum oxide nano-channel film to face to the open pore, and sealing the peripheries of the two plates by using a polytetrafluoroethylene adhesive tape;
s4, soaking and etching: adding 3, 5-pyrazole dicarboxylic acid monohydrate with the concentration of 0.03mol/L and 0.05 mol/L sodium hydroxide aqueous solution into a reaction kettle, immersing the die packaged in the step S3 into the reaction kettle, sealing the reaction kettle, and standing for 4 hours;
s5, hydrothermal self-growth: heating the reaction kettle to 98 ℃ for hydrothermal synthesis reaction for 48 hours, and cooling to room temperature after the reaction to obtain the MOF-303/AAO composite membrane.
The beneficial effects of the invention are illustrated by the following experiments:
experimental example 1: a method for preparing a MOF-303/AAO composite film by hydrothermal self-growth, which specifically comprises the following steps:
s1, manufacturing a die: taking two polytetrafluoroethylene plates with the same size, wherein the specification is 22 multiplied by 3 mm, the middle part of one polytetrafluoroethylene plate is provided with a round hole, and the diameter of the hole is 12 mm, as shown in 1 in fig. 8;
s2, pretreatment of a matrix film: cutting a porous anodic aluminum oxide nano-channel membrane with the aperture of 110-150nm to be the same as the polytetrafluoroethylene plate in size and attaching, and respectively and sequentially ultrasonically cleaning the porous anodic aluminum oxide nano-channel membrane for 30s by using acetone, absolute ethyl alcohol and deionized water and drying;
s3, packaging: placing the pretreated porous anodic aluminum oxide nano-channel film between two polyethylene plates, and sealing the periphery of the two plates by using polytetrafluoroethylene adhesive tape with the bottom side of the porous anodic aluminum oxide nano-channel film facing to the open pore, as shown in 2 in fig. 8;
s4, soaking and etching: dissolving 0.1 g sodium hydroxide in 45 mL deionized water, adding 0.2223 g of 3, 5-pyrazole dicarboxylic acid monohydrate after complete dissolution, stirring by ultrasonic until the 3, 5-pyrazole dicarboxylic acid monohydrate is completely dissolved, and adding 1 mL hydrochloric acid with the concentration of 1mol/L to obtain a hydrothermal reaction solution; adding an aqueous solution into the reaction kettle, vertically immersing the die packaged in the step S3 into the reaction kettle, sealing the reaction kettle, and standing for 7h;
s5, hydrothermal self-growth: heating the reaction kettle to 100 ℃ for hydrothermal synthesis reaction, wherein the reaction time is 48 hours, cooling to room temperature after the reaction, removing the die, repeatedly flushing with deionized water until no particle MOF-303 remains on the surface of the film, and drying to obtain the MOF-303/AAO composite film.
Experimental example 2: a method for preparing pure MOF-303 powder by using water heat is carried out according to the following steps:
(1) Preparing a hydrothermal reaction liquid: dissolving 0.1 g sodium hydroxide in 45 mL deionized water, adding 0.3 g aluminum trichloride after complete dissolution, then adding 0.2223 g 3, 5-pyrazoledicarboxylic acid monohydrate, and stirring by ultrasonic until the solution is completely dissolved to obtain a MOF-303 hydrothermal reaction solution;
(2) Hydrothermal synthesis: pouring the prepared hydrothermal reaction liquid into a hydrothermal reaction kettle with the volume of 100 mL, sealing, heating to 100 ℃ in an electric heating oven, preserving heat for 48h, and cooling to room temperature along with a furnace;
(3) And (3) centrifugal precipitation: pouring the reacted hydrothermal solution into a centrifuge tube, centrifuging at 9000 rpm for 5 min, collecting white precipitate, and centrifuging with deionized water under the same conditions for 3 times;
(4) And (3) drying: and after centrifugation, placing the collected white precipitate in an electric heating oven, and drying at 60 ℃ for 12 h to obtain pure MOF-303 powder.
The MOF-303/AAO composite film prepared in the experimental example 1 is scanned, the plan view of a scanning electron microscope is shown in fig. 2, the sectional view of the scanning electron microscope is shown in fig. 3, and the graph shows that a uniform and compact MOF-303 crystal layer almost without defects is covered on the surface of the AAO, the MOF-303 layer is uniform in thickness and free from larger fluctuation, the MOF-303 on the wall of the AAO pore canal grows depending on the trend of the pore canal, and the regularity of the AAO pore canal is structurally reserved.
The pure MOF-303 powder prepared in the experimental example 2 is subjected to electron microscope scanning, and as shown in fig. 4, the MOF-303 crystal grains are in a regular cube shape, have uniform size and are unified with the morphology of the MOF-303 grown on the AAO base film.
Subjecting MOF-303/AAO composite film prepared in experimental example 1, AAO film and pure MOF-303 powder prepared in experimental example 2 to Fourier infrared analysis, respectively, wherein the spectrum is shown in FIG. 5, and the spectrum of pure MOF-303 powder is shown in 1001 and 1001 cm −1 、1478 cm −1 And 1529 cm −1 The peaks at 1386 and cm demonstrate vibrations of the N-NH, C-C and C-N bonds, respectively −1 And 1604 cm −1 Where evidence of coordinated carboxyl groups was found, H was verified 3 PDC ligand and Al 3+ Is a combination of (a) and (b). As can be seen by comparing the spectrograms of the AAO film and the MOF-303 powder, the composite film is formed in 1386 and 1386 cm −1 And 1604 cm −1 The characteristic peak of MOF-303 at 2345 and cm is obvious −1 The positions correspond to the characteristic peaks of the AAO film, which fully explainMOF-303 grows efficiently on AAO films.
Subjecting the MOF-303/AAO composite film prepared in experimental example 1, the AAO film and the pure MOF-303 powder prepared in experimental example 2 to X-ray diffraction, wherein the diffraction diagram is shown in figure 6, 1 represents the MOF-303/AAO composite film, 2 represents the pure MOF-303 powder and 3 represents the AAO film; as is clear from the XRD pattern of pure MOF-303 powder represented by 2, the crystallinity of MOF-303 is high, the crystal face orientation is single, the highest peak corresponding to the 2theta angle of 8.7 degrees is a characteristic peak, the characteristic peak is obvious in the XRD pattern of the MOF-303/AAO composite film, and the MOF-303 is firmly supported on the AAO film. 3 shows the characteristic of the amorphous structure of the AAO film, and the characteristic is also shown in the XRD image of the MOF-303/AAO composite film, which proves that the AAO film does not completely participate in the growth of the MOF-303 in the preparation process of the composite film, but retains the structure of the AAO film, and provides basic support for the stable existence of the composite film.
EDS energy spectrum and atomic percent cake diagram are made for the MOF-303/AAO composite film prepared in experimental example 1, as shown in fig. 7, according to EDS energy spectrum, the C, N, O, al four elements are uniformly distributed, C, N elements are derived from organic ligands, and obvious specific gravity is occupied in the cake diagram, so that the MOF-303 successfully grows and adheres to the AAO film.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art who is skilled in the art to which the present invention pertains will appreciate that the technical scheme and the inventive concept according to the present invention are equally substituted or changed within the scope of the present invention.
Claims (5)
1. A method for preparing MOF-303/AAO composite membrane by hydrothermal self-growth is characterized in that porous anodic alumina nano channel membrane is taken as a substrate, aqueous solution of 3, 5-pyrazole dicarboxylic acid monohydrate, sodium hydroxide or/and hydrochloric acid is taken as a reaction solution, and hydrothermal synthesis reaction is carried out at 80-120 ℃ to prepare MOF-303/AAO composite membrane;
the preparation method specifically comprises the following steps:
s1, manufacturing a die: taking two polytetrafluoroethylene plates with the same size, wherein a round hole is formed in the middle of one polytetrafluoroethylene plate;
s2, pretreatment of a matrix film: cutting the porous anodic aluminum oxide nano channel membrane to be the same as the polytetrafluoroethylene plate in size and attaching, and cleaning and drying the porous anodic aluminum oxide nano channel membrane by using acetone, absolute ethyl alcohol and deionized water in sequence respectively;
s3, packaging: placing the pretreated porous anodic aluminum oxide nano-channel film between two polyethylene plates, enabling the bottom side of the porous anodic aluminum oxide nano-channel film to face to the open pore, and sealing the peripheries of the two plates by using a polytetrafluoroethylene adhesive tape;
s4, soaking and etching: adding a reaction solution into the reaction kettle, immersing the die packaged in the step S3 into the reaction kettle, sealing the reaction kettle and standing;
s5, hydrothermal self-growth: heating the reaction kettle to carry out hydrothermal synthesis reaction, and cooling to room temperature after the reaction to obtain the MOF-303/AAO composite film;
wherein the concentration of hydrochloric acid in the reaction solution is 0-0.0217 mol/L, the concentration of sodium hydroxide is 0-0.05556 mol/L, and the concentration of 3, 5-pyrazoledicarboxylic acid monohydrate is 0.01-0.03 mol/L; the pore diameter of the porous anodic aluminum oxide nano channel membrane is less than 200nm.
2. The method for preparing the MOF-303/AAO composite film according to claim 1, wherein the hydrothermal synthesis reaction time is 24-56 h.
3. The method for preparing a MOF-303/AAO composite film according to claim 1, wherein the time for standing in the step S4 is 0 to 8 hours.
4. A MOF-303/AAO composite membrane prepared according to the method of claim 1.
5. Use of the MOF-303/AAO composite membrane of claim 4 in directional rapid filtration.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101912737A (en) * | 2010-08-26 | 2010-12-15 | 南京工业大学 | Method for preparing metal organic framework supported film |
| CN106861649A (en) * | 2015-12-14 | 2017-06-20 | 北京化工大学 | A kind of desulfurizing oil adsorbent based on metal-organic framework compound and preparation method thereof |
| CN107629216A (en) * | 2017-10-01 | 2018-01-26 | 桂林理工大学 | The Sm MOF materials and preparation method constructed using 3,5 pyrazoles dicarboxylic acids as part |
| CN108939958A (en) * | 2017-05-27 | 2018-12-07 | 南京工业大学 | Method for improving gas separation performance of supported MOF (metal organic framework) membrane by utilizing polymer coating |
| CN113713635A (en) * | 2021-06-22 | 2021-11-30 | 天津大学 | Metal organic framework ZIF-8 composite membrane containing amino ligand, preparation and application thereof |
| WO2021245464A1 (en) * | 2020-06-04 | 2021-12-09 | Kyoto University | Graphene oxide-nanoparticle composite membranes, preparation and uses thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005012087A1 (en) * | 2005-03-16 | 2006-09-21 | Basf Ag | Liquid absorption by organometallic frameworks |
| CN103977715B (en) * | 2014-05-12 | 2015-12-09 | 北京航空航天大学 | A kind of preparation method of MIL-53 metal organic framework film material of independent self-supporting |
| WO2016014963A1 (en) * | 2014-07-24 | 2016-01-28 | King Abdullah University Of Science And Technology | Fabrication of highly co2 selective metal organic framework membrane using liquid phase epitaxy approach |
| CN105879715A (en) * | 2014-12-16 | 2016-08-24 | 天津工业大学 | Preparation method for metal organic skeleton film on polyether sulfone support |
| CN105588860B (en) * | 2015-12-13 | 2018-09-28 | 中国科学院福建物质结构研究所 | Transition metal oxide surface heterogeneous medium epitaxial metal organic frame shell and its preparation method and application |
| GB201805261D0 (en) * | 2018-03-29 | 2018-05-16 | G20 Water Tech Limited | Membranes |
| US11478744B2 (en) * | 2018-08-09 | 2022-10-25 | King Fahd University Of Petroleum And Minerals | Gas separation membrane containing metal-organic frameworks and methods of making thereof |
| EP3718621B1 (en) * | 2018-08-16 | 2023-05-10 | Commonwealth Scientific and Industrial Research Organisation | Metal organic framework based water capture apparatus |
| CN112827369B (en) * | 2021-01-18 | 2021-11-09 | 蓝星（杭州）膜工业有限公司 | Preparation method of nano hybrid composite membrane |
-
2022
- 2022-07-18 CN CN202210839865.1A patent/CN115178107B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101912737A (en) * | 2010-08-26 | 2010-12-15 | 南京工业大学 | Method for preparing metal organic framework supported film |
| CN106861649A (en) * | 2015-12-14 | 2017-06-20 | 北京化工大学 | A kind of desulfurizing oil adsorbent based on metal-organic framework compound and preparation method thereof |
| CN108939958A (en) * | 2017-05-27 | 2018-12-07 | 南京工业大学 | Method for improving gas separation performance of supported MOF (metal organic framework) membrane by utilizing polymer coating |
| CN107629216A (en) * | 2017-10-01 | 2018-01-26 | 桂林理工大学 | The Sm MOF materials and preparation method constructed using 3,5 pyrazoles dicarboxylic acids as part |
| WO2021245464A1 (en) * | 2020-06-04 | 2021-12-09 | Kyoto University | Graphene oxide-nanoparticle composite membranes, preparation and uses thereof |
| CN113713635A (en) * | 2021-06-22 | 2021-11-30 | 天津大学 | Metal organic framework ZIF-8 composite membrane containing amino ligand, preparation and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Achieving efficient proton conduction in a MOF-based proton exchange membrane through an encapsulation strategy;.Yuan Yuan Cai .Qian Yang .Qing Lin Liu;《Journal of Membrane Science》;第590卷;第1-6页 * |
| 二维金属有机骨架的合成、结构与应用;章家立;《华东交通大学学报》;第37卷(第6期);第9-16页 * |
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